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Publication numberUS20050064282 A1
Publication typeApplication
Application numberUS 10/943,857
Publication dateMar 24, 2005
Filing dateSep 20, 2004
Priority dateSep 24, 2003
Also published asUS7910247, US20100143790
Publication number10943857, 943857, US 2005/0064282 A1, US 2005/064282 A1, US 20050064282 A1, US 20050064282A1, US 2005064282 A1, US 2005064282A1, US-A1-20050064282, US-A1-2005064282, US2005/0064282A1, US2005/064282A1, US20050064282 A1, US20050064282A1, US2005064282 A1, US2005064282A1
InventorsHiroki Inagaki, Yoshinao Tatebayashi, Norio Takami
Original AssigneeHiroki Inagaki, Yoshinao Tatebayashi, Norio Takami
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Nonaqueous electrolyte battery
US 20050064282 A1
Abstract
A nonaqueous electrolyte battery includes a case, a nonaqueous electrolyte provided in the case, a positive electrode provided in the case, and a negative electrode provided in the case, including a negative electrode active material and an electronic conductor containing a carbonaceous material, wherein a negative electrode working potential is nobler at least 1 V than a lithium electrode potential, and the carbonaceous material has a spacing (d002) of (002) plane of 0.344 nm or more and 0.352 nm or less, and a crystallite size (Lc) in the C-axis direction of 10 nm or less.
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Claims(17)
1. A nonaqueous electrolyte battery comprising:
a case;
a nonaqueous electrolyte provided in the case;
a positive electrode provided in the case; and
a negative electrode provided in the case, including a negative electrode active material and an electronic conductor containing a carbonaceous material,
wherein a negative electrode working potential is nobler at least 1 V than a lithium electrode potential, and the carbonaceous material has a spacing (d002) of (002) plane of 0.344 nm or more and 0.352 nm or less, and a crystallite size (Lc) in the C-axis direction of 10 nm or less.
2. The nonaqueous electrolyte battery according to claim 1, wherein the crystallite size (Lc) in the C-axis direction is 0.1 nm or more and 10 nm or less.
3. The nonaqueous electrolyte battery according to claim 1, wherein the spacing (d002) is 0.345 nm or more and 0.35 nm or less.
4. The nonaqueous electrolyte battery according to claim 1, wherein an average particle size of the carbonaceous material is 0.1 μm or more and 10 μm or less.
5. The nonaqueous electrolyte battery according to claim 1, wherein the carbonaceous material has a cumulative volume distribution in which 10% particle size D10 is 0.1 μm or more and 10 μm or less, 50% particle size D50 is 5 μm or more and 20 μm or less, and 90% particle size D90 is 10 μm or more and 30 μm or less.
6. The nonaqueous electrolyte battery according to claim 1, wherein a specific surface area of the carbonaceous material is 10 m2/g or more and 100 m2/g or less.
7. The nonaqueous electrolyte battery according to claim 1, wherein the negative electrode active material includes lithium titanate particles.
8. The nonaqueous electrolyte battery according to claim 7, wherein an average primary particle size of the lithium titanate particles is 1 μm or less.
9. The nonaqueous electrolyte battery according to claim 7, wherein a composition of the lithium titanate particles is expressed as Li4+xTi5O12, where x is in a range of 0≦x≦3.
10. The nonaqueous electrolyte battery according to claim 1, wherein the case is formed of a sheet of 0.5 mm or less in thickness.
11. The nonaqueous electrolyte battery according to claim 1, wherein the negative electrode further contains a binder.
12. The nonaqueous electrolyte battery according to claim 1, wherein the nonaqueous electrolyte further contains a lithium salt.
13. A nonaqueous electrolyte battery comprising:
a case;
a nonaqueous electrolyte provided in the case;
a positive electrode provided in the case; and
a negative electrode provided in the case, including a negative electrode active material and an electronic conductor containing a carbonaceous material,
wherein the negative electrode active material contains at least one compound selected from the group consisting of tungsten oxide, molybdenum oxide, iron sulfide, titanium sulfide, and composite oxide containing lithium and titanium, and the carbonaceous material has a spacing (d002) of (002) plane of 0.344 nm or more and 0.352 nm or less, and a crystallite size (Lc) in the C-axis direction of 10 nm or less.
14. The nonaqueous electrolyte battery according to claim 13, wherein the crystallite size (Lc) in the C-axis direction is 0.1 nm or more and 10 nm or less, and the spacing (d002) is 0.345 nm or more and 0.35 nm or less.
15. The nonaqueous electrolyte battery according to claim 13, wherein the carbonaceous material has a cumulative volume distribution in which 10% particle size D10 is 0.1 μm or more and 10 μm or less, 50% particle size D50 is 5 μm or more and 20 μm or less, and 90% particle size D90 is 10 μm or more and 30 μm or less.
16. The nonaqueous electrolyte battery according to claim 13, wherein a composition of the composite oxide containing lithium and titanate is expressed as Li4+xTi5O12, where x is in a range of 0≦x≦3.
17. The nonaqueous electrolyte battery according to claim 13, wherein a composition of the iron sulfide is expressed as FeSx, where x is in a range of 1.08≦x≦1.33.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based upon and claims the benefit of priority from prior Japanese Patent Application No. 2003-332109, filed Sep. 24, 2003, the entire contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a nonaqueous electrolyte battery. The invention is applicable to both a nonaqueous electrolyte primary battery and a nonaqueous electrolyte secondary battery.

2. Description of the Related Art

Electronic appliances are becoming smaller in size and lighter in weight recently owing to rapid technical progress in the field of electronics. As a result, cordless and portable electronic appliances are being more prevalent, and secondary batteries used as a driving source are demanded to be smaller in size, lighter in weight, and higher in energy density. To meet such demands, lithium secondary batteries of high energy density are being developed. Lately, ultrathin lightweight secondary batteries using a case of laminate film containing aluminum are being developed and sold on market.

The secondary battery using a case of a laminate film containing aluminum changes in battery thickness due to volume expansion and contraction of an electrode by charging and discharging. As a result, the battery may be deformed, the electrode interval widened, which increases the battery resistance, thus the battery characteristics may be lowered.

To avoid such problems, negative electrode active materials are proposed in Jpn. Pat. Appln. KOKAI Publication No. 9-199179. In the publication, the negative electrode active material is made of lithium titanate or a carbon material of which spacing of (002) plane by an X-ray wide angle diffraction method is 3.7 Å or more, whereby it is intended to decrease expansion and contraction of the electrode due to reversible intercalation and deintercalation of lithium, thereby reducing expansion of an electrode group. Lithium titanate is hardly changed in volume due to charging and discharging, and is hence very small in change of battery thickness. By using this compound in the negative electrode active material, the above problems can be solved.

However, since lithium titanate is poor in conductivity, when the negative electrode is manufactured without adding an electronic conductor as in the publication, the battery is inferior under heavy currents. When the conductivity of the negative electrode active material is low, by adding an electronic conductor made of carbon material to the negative electrode active material, it is known that the high rate characteristic is improved. However, in a nonaqueous electrolyte battery having a negative electrode containing an electronic conductor made of a carbon material and lithium titanate, when the battery is stored in a high temperature environment, or when charging and discharging operation is repeated in a high temperature environment, the electronic conductor reacts with an electrolysis solution, and a large volume of gas is generated, thus the battery characteristics are extremely lowered.

BRIEF SUMMARY OF THE INVENTION

It is an object of the invention to provide a nonaqueous electrolyte battery excellent in charging and discharging characteristics in a high temperature environment, and high in safety and reliability.

According to a first aspect of the present invention, there is provided a nonaqueous electrolyte battery comprising:

    • a case;
    • a nonaqueous electrolyte provided in the case;
    • a positive electrode provided in the case; and
    • a negative electrode provided in the case, including a negative electrode active material and an electronic conductor containing a carbonaceous material,
    • wherein a negative electrode working potential is nobler at least 1 V than a lithium electrode potential, and the carbonaceous material has a spacing (d002) of (002) plane of 0.344 nm or more and 0.352 nm or less, and a crystallite size (Lc) in the C-axis direction of 10 nm or less.

According to a second aspect of the present invention, there is provided a nonaqueous electrolyte battery comprising:

    • a case;
    • a nonaqueous electrolyte provided in the case;
    • a positive electrode provided in the case; and
    • a negative electrode provided in the case, including a negative electrode active material and an electronic conductor containing a carbonaceous material,
    • wherein the negative electrode active material contains at least one compound selected from the group consisting of tungsten oxide, molybdenum oxide, iron sulfide, titanium sulfide, and composite oxide containing lithium and titanium, and the carbonaceous material has a spacing (d002) of (002) plane of 0.344 nm or more and 0.352 nm or less, and a crystallite size (Lc) in the C-axis direction of 10 nm or less.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

The single FIGURE is a partially cut-away perspective view of a nonaqueous electrolyte battery according to an embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

In a negative electrode containing a carbonaceous material that intercalates and deintercalates lithium as a negative electrode active material, it is known that a protective film, called a solid electrolyte interface (SEI), is formed on the negative electrode surface at the time of initial charge. However, in a nonaqueous electrolyte battery having a negative electrode containing a negative electrode active material, such as lithium titanate, which imperts a negative electrode working potential nobler at least 1 V than a lithium electrode potential, even if a carbonaceous material is contained as an electronic conductor in the negative electrode, the reaction of forming the protective film does not take place, so that the carbonaceous material of the negative electrode and nonaqueous electrolyte react in a high temperature environment, and gas generation is increased in a high temperature environment, as studied and disclosed by the present inventors.

In the negative electrode containing acetylene black or carbon black as an electronic conductor and the negative electrode active material such as lithium titanate, the negative electrode working potential is nobler at least 1 V than the lithium electrode potential. Since the particle size of acetylene black and carbon black is small, aggregation is like to occur in the negative electrode. Accordingly, the electronic conductor does not disperse uniformly in the active material, and current collection failure is likely to occur. Since such an electronic conductor has many functional groups on its surface and a large specific surface area, it is likely to react with the electrolysis solution, thereby promoting gas generation in a high temperature environment.

The inventors have conducted further research, and discovered that gas generation in a high temperature environment can be suppressed even if a protective film is not formed, while obtaining high conductivity, by specifying both a spacing d002 of (002) plane and a crystallite size Lc in the C-axis direction of a carbonaceous material within specific ranges.

The carbonaceous material used in an embodiment of the invention is specified as follows: the spacing (d002) of (002) plane is 0.344 nm or more and 0.352 nm or less, and the crystallite size (Lc) in the C-axis direction is 10 nm or less. The carbonaceous material having such properties is less likely to aggregate and more likely to mix easily with the negative electrode active material in the solvent, as compared with acetylene black and carbon black of which spacing or crystallite size is outside the specified range. Therefore, a conductive network can be favorably built up in the negative electrode, and a nonaqueous electrolyte battery having an excellent high rate characteristic can be realized. Further, the carbonaceous material does not react with a nonaqueous electrolyte even in a high temperature environment, and gas generation can be suppressed, so that even in a flat battery having a laminate film case which is more likely to be deformed than a metal case, battery deformation does not occur, and a favorable battery performance can be maintained.

The reason for defining the spacing (d002) and crystallite size Lc in the specified ranges will be more specifically explained below. Even at the crystallite size Lc of 10 nm or less, if the spacing (d002) is less than 0.344 nm, the reactivity is increased between the nonaqueous electrolyte and an edge surface of a carbon layer composing a graphite crystallite, so that the gas generation increases in high temperature storage. On the other hand, if the spacing (d002) exceeds 0.352 nm, surface functional groups increase in number, and the functional groups react with the nonaqueous electrode in high temperature storage, so that the gas generation also increases in high temperature storage. A more preferred range of the spacing (d002) is 0.345 nm or more and 0.35 nm or less.

Even when the spacing (d002) is 0.344 nm or more and 0.352 nm or less, if the crystallite size Lc exceeds 10 nm, the reactivity between the nonaqueous electrolyte and the edge surface of the carbon layer increases, so that the gas generation increases in high temperature storage. If the crystallite size Lc is less than 0.1 nm, since growth of the graphite structure is insufficient, the conductivity may be insufficient, and surface functional groups of the carbonaceous material may increase. Accordingly, the crystallite size Lc is preferred to be 0.1 nm or more and 10 nm or less, and a more preferable range is 1 nm or more and 3 nm or less.

The average particle size of the carbonaceous material is preferred to be 0.1 μm or more in order to suppress gas generation effectively. To build a favorable conductive network, the average particle size of the carbonaceous material is preferred to be 10 μm or less.

The specific surface area of the carbonaceous material is preferred to be 10 m2/g or more in order to build a favorable conductive network. To suppress gas generation effectively, the specific surface area of the carbonaceous material is preferred to be 100 m2/g or less.

An embodiment of a nonaqueous electrolyte battery according to the invention will be described below.

The nonaqueous electrolyte battery comprises an electrode group including a positive electrode, a negative electrode, a separator provided between the positive electrode and the negative electrode, a nonaqueous electrolyte held in the electrode group, and a case for accommodating the electrode group.

The positive electrode, negative electrode, separator, nonaqueous electrolyte, and case will be specifically described below.

1) Positive Electrode

The positive electrode comprises a positive electrode current collector, and a positive electrode layer provided on one side or both sides of the positive electrode current collector. The positive electrode layer includes an active material and a binder.

The positive electrode current collector can be made of, for example, aluminum or aluminum alloy.

The positive electrode active material can be made of various oxides, sulfides and the like. Examples of the positive electrode active material include manganese dioxide (MnO2), iron oxide, copper oxide, nickel oxide, lithium manganese composite oxide such as LixMn2O4 or LixMnO2, lithium nickel composite oxide such as LixNiO2, lithium cobalt composite oxide such as LixCoO2, lithium nickel cobalt composite oxide such as LiNi1-yCOyO2, lithium manganese cobalt composite oxide such as LiMnyCo1-yO2, spinel type lithium manganese nickel composite oxide such as LixMn2-yNiyO4, lithium phosphorus oxide having an olivine structure such as LixFePO4, LixFe1-yMnyPO4, LixCoPO4, iron sulfate such as Fe2(SO4)3, and vanadium oxide such as V2O5. Values of x and y are preferred to be in a range of 0 to 1. Other examples include a conductive polymer material such as polyaniline and polypyrrole, a disulfide polymer material, sulfur (S), an organic material such as carbon fluoride, and an inorganic material.

Since a preferred positive electrode active material is desired to have a high positive electrode voltage, preferred examples include lithium manganese composite oxide such as LixMn2O4, lithium nickel composite oxide, lithium cobalt composite oxide, lithium nickel cobalt composite oxide, spinel type lithium manganese nickel composite oxide, lithium manganese cobalt composite oxide, and lithium iron phosphate such as LixFePO4.

As the electronic conductor, for example, acetylene black, carbon black, and graphite can be used.

As the binder, for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and fluororubber can be used.

The blending ratio of the positive electrode active material, the electronic conductor, and the binder is 80 to 95 wt. % of the positive electrode active material, 3 to 18 wt. % of the electronic conductor, and 2 to 17 wt. % of the binder.

2) Negative Electrode

The negative electrode comprises a negative electrode current collector, and a negative electrode layer provided on one side or both sides of the negative electrode current collector. The negative electrode layer contains a negative electrode active material which imperts a negative electrode working potential nobler at least 1 V than a lithium electrode potential.

The negative electrode current collector can be made of aluminum or aluminum alloy.

The negative electrode active material contains a material which imperts a negative electrode working potential nobler at least 1 V vs. Li/Li+. Examples of such a negative electrode active material include tungsten oxide, molybdenum oxide, iron sulfide, titanium sulfide, and composite oxides containing lithium and titanium such as lithium titanate. In particular, lithium titanate is excellent in cycle characteristic, and among others lithium titanate that has a spinel structure and a chemical formula Li4+xTi5O2 (0≦x≦3) is preferred. The potential difference between the negative electrode working potential and the lithium electrode potential is preferred to be 1 V or more and 2 V or less. The negative electrode active material can be composed of one type or two or more types.

The specific surface area of lithium titanate is preferred to be 1 to 10 m2/g. The specific surface area is measured by a BET method. The reason is explained below. If the specific surface area is less than 1 m2/g, the effective area of the active material contributing to electrode reaction is small, and the high rate discharge characteristic may decline. If the specific surface area exceeds 10 m2/g, the reaction of the negative electrode active material and electrolyte increases, so that the charge and discharge efficiency may decline or gas generation in storage may be promoted.

Among iron sulfides, FeSx (molar ratio x denotes 1.08≦x≦1.33) is preferred. In particular, FeSx of which the molar ratio x is in a range of 1.08≦x≦1.2 is preferred because the high capacity and long cycle life of a secondary battery can be established at the same time. A more preferred range of the molar ratio x is 1.09 or more and 1.12 or less.

Among FeSx compounds, preferred examples are Fe9S10(FeS1.11), Fe10S11(FeS1.1), and Fe11S12(FeS1.09).

The average primary particle size of the negative electrode active material is preferred to be 1 μm or less. As a result, the cycle performance can be enhanced. This effect is particularly notable in high rate discharge. This is because, in the negative electrode active material for intercalating and deintercalating lithium ions, the lithium ion diffusion distance in the active material is shorter when the primary particle size is smaller, and hence the specific surface area increases. A more preferred average primary particle size is 0.3 μm or less. However, if the primary particle size is too small, primary particles are likely to aggregate, and the negative electrode held the nonaqueous electrolyte too much, thereby causing depletion of the electrolyte at the positive electrode. Accordingly, the lower limit is preferred to be 0.001 μm.

The negative electrode layer further contains an electronic conductor. The electronic conductor includes a carbonaceous material. The carbonaceous material is preferred to have a spacing (d002) of (002) plane of 0.344 nm or more and 0.352 nm or less, and crystallite size (Lc) in the C-axis direction of 10 nm or less.

The type of the carbonaceous material is not particularly specified, but it is preferred to be derived from coke, rather than carbon black and acetylene black.

The carbonaceous material, such as coke, can intercalate and/or deintercalate lithium. And the carbonaceous material that is not capable to intercalate and deintercalate lithium can be used.

The average particle size of the carbonaceous material is preferred to be 0.1 μm or more in order to suppress gas generation effectively. To build a favorable conductive network, the average particle size of the carbonaceous material is preferred to be 10 μm or less. By controlling the average particle size of the carbonaceous material in a range of 0.1 μm or more and 10 μm or less, a favorable high temperature characteristic can be realized.

In order to enhance the high rate characteristic while maintaining a favorable high temperature performance, the carbonaceous material is preferred to have a particle size distribution in the following range.

The particle size distribution of the carbonaceous material is obtained by integrating the volume from smaller particle sizes. The particle size distribution is preferred to satisfy the following conditions of (a) to (c). Incidentally, the integrated volume is defined as 100%.

    • (a) A particle size D10 is a particle size that gives 10% of the integrated volume. The particle size D10 can be 0.1 μm or more and 10 μm or less.
    • (b) A particle size D50 is a particle size that gives 50% of the integrated volume. The particle size D50 can be 5 μm or more and 20 μm or less.
    • (c) A particle size D90 is a particle size that gives 90% of the integrated volume. The particle size D90 can be 10 μm or more and 30 μm or less.

If D90 is lower than 10 μm, the carbonaceous material is buried in the space between the negative electrode active material particles, the diffusion resistance of electrons in the thickness direction of the electrode increases, and the high rate characteristic may decline. On the other hand, if D90 is more than 30 μm, the contact area of the carbonaceous material and the negative electrode active material decreases, and also the diffusion resistance of electrons in the thickness direction of the electrode increases, so that the high rate characteristic may decline. A more preferred range of D90 is 12 μm or more and 20 μm or less.

While D90 is in a range of 10 μm or more and 30 μm or less, if D10 is more than 10 μm, the particle size difference between large particles and small particle is small. Therefore, very few particles gather on one particle, a conductive network is not built sufficiently, and the diffusion resistance of electrons in the thickness direction of the electrode may increase. On the other hand, if D10 is less than 0.1 μm, the reactivity of the carbonaceous material with the nonaqueous electrolyte is increased, and gas generation in a high temperature environment may be increased.

A more preferred range of D10 is 1 μm or more and 3 μm or less.

In the range of D90 to 10 μm or more and 30 μm or less and D10 of 0.1 μm or more and 10 μm or less, if D50 is more than 20 μm, the particle size distribution concentrates on large particle sizes. Therefore, only large particles gather around large particles, the diffusion resistance of electrons may increase in the thickness direction of the electrode. On the other hand, in the range of D90 to 10 μm or more and 30 μm or less and D10 of 0.1 μm or more and 10 μm or less, if D50 is less than 5 μm, the particle size distribution concentrates on small particle sizes. As a result, the electron diffusion route of each particle is short, and electrons are diffused through many particles. Therefore, the diffusion resistance of electrons may increase in the thickness direction of the electrode. A more preferred range of D50 is 7 μm or more and 15 μm or less.

The profile of particle size distribution satisfying the conditions of (a) to (c) is broad, and particles are present uniformly from a small size to a large size. Therefore, multiple particles gather around one particle, and the electron diffusion route can be formed like a network on the electrode. Further, since large particles are present in an appropriate amount, electrons can be diffused promptly in the thickness direction of the electrode. As a result, the diffusion path of electrons in the thickness direction of the electrode is formed favorably, and diffusion resistance of electrons in the thickness direction of electron can be lowered, so that the high rate characteristic of the nonaqueous electrolyte battery can be enhanced.

The specific surface area of the carbonaceous material is preferred to be 10 m2/g or more in order to build a favorable conductive network. To suppress gas generation effectively, the specific surface area of the carbonaceous material is preferred to be 100 m2/g or less.

The effect of the invention is achieved as far as the electronic conductor is mainly made of the carbonaceous material, that is, more than 50 wt. % of the electronic conductor is the carbonaceous material. In the electronic conductor, acetylene black or graphite can be added at a rate not exceeding 50 wt. % of the electronic conductor components.

A binder can be contained in the negative electrode layer. Such a binder can include, for example, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and fluororubber.

The blending ratio of the negative electrode active material, the electronic conductor, and the binder is 70 to 96 wt. % of the negative electrode active material, 2 to 28 wt. % of the electronic conductor, and 2 to 28 wt. % of the binder. If the electronic conductor is contained at less than 2 wt. %, the current collecting performance is lowered, and the high rate characteristic may decline. If the binder is contained at less than 2 wt. %, the binding strength of the compound layer and current collector is lowered, and the cycle performance may drop. On the other hand, from the viewpoint of high capacity, the content each of the electronic conductor and binder is preferred to be 28 wt. % or less.

The negative electrode can be manufactured, for example, by suspending the negative electrode active material, electronic conductor and binder in a proper solvent, applying this suspension on a current collector of aluminum foil or the like, and drying and pressing.

3) Separator

The separator is, for example, a porous separator.

The porous separator is, for example, a porous film including polyethylene, polypropylene, cellulose, or polyvinylidene fluoride (PVdF), a synthetic resin nonwoven fabric, and the like. In particular, a porous film made of polyethylene or polypropylene, or both of them may be preferred because the safety of the secondary battery can be enhanced.

4) Nonaqueous Electrolyte

Examples of the nonaqueous electrolyte include a liquid nonaqueous electrolyte prepared by dissolving an electrolyte in an organic solvent, and others including lithium salt and room temperature molten salt.

A nonaqueous electrolyte will be explained below.

Examples of the electrolyte include lithium perchlorate (LiClO4), lithium hexfluoro phosphate (LiPF6), lithium tetrafluoro borate (LiBF4), lithium hexfluoro arsenate (LiAsF6), lithium trifluoromethasulfonate (LiCF3SO3), bis-trifluoromethyl sulfonyl imide lithium [LiN(CF3SO2)2], and other lithium salts. The electrolyte is preferred to be dissolved in a range of 0.5 to 2 mol/L in an organic solvent.

Examples of the organic solvent can include cyclic carbonate such as ethylene carbonate (EC), propylene carbonate (PC) or vinylene carbonate (VC); chain carbonate such as dimethyl carbonate (DMC), methyl ethyl carbonate (MEC), or diethyl carbonate (DEC); cyclic ether such as tetrahydrofurane (THF) or 2-methyl tetrahydrofurane (2MeTHF); chain ether such as dimethoxy ethane (DME); γ-butyrolactone (BL), acetonitrile (AN), and sulfolane (SL). These organic solvents may be used either alone or as mixture of two- or more types.

A nonaqueous electrolyte containing lithium salt and room temperature molten salt will be explained below.

The room temperature molten salt is a salt which is liquid at least in part at room temperature, and the room temperature refers to a range of temperature assumed within normal operation of a power source. Such a temperature range assumed to be in a normal operating range of the power source is about 120 C. or about 60 C. at the upper limit depending on the case, and about −40 C. or about −20 C. at the lower limit depending on the case.

The lithium salt is a lithium salt that has a wide potential window and is generally used in a lithium secondary battery. Examples include LiBF4, LiPF6, LiClO4, LiCF3SO3, LiN(CF3SO2)2, LiN(C2F5SO2), LiN(CF3SC(C2F5SO2)3, etc., but are not limited to them alone. They can be used either alone or as mixture of two or more types.

The content of the lithium salt in the nonaqueous electrolyte is preferred to be 0.1 to 3 mol/L. The reason is as follows. If the content of the lithium salt is less than 0.1 mol/L, the ion conductivity of the nonaqueous electrolyte is lowered, and high rate current and low temperature discharge characteristic may not be obtained. If the content of the lithium salt exceeds 3 mol/L, the melting point of the nonaqueous electrolyte is raised, and it is hard to maintain a liquid form at room temperature. A more preferred range of the lithium salt content is 1 to 2 mol/L.

The room temperature molten salt has a quaternary ammonium organic cation having a skeleton shown in chemical formula (1). Or it can have an imidazolium cation having a skeleton shown in chemical formula (2).


where R1 and R2 are CnH2n+1 (n=1 to 6), which can be either equal or different, and R3 is H or CnH2n+1 (n=1 to 6).

The quaternary ammonium organic cation having the skeleton shown in chemical formula (1) includes imidazolium ion such as dialkyl imidazolium and trialkyl imidazolium, tetraalkylammonium ion, alkylpyridinium ion, pyrazolium ion, pyrolidinium ion, piperidinium ion, etc. In particular, the imidazolium cation having the skeleton shown in chemical formula (2) is preferred.

The tetraalkyl ammonium ion includes trimethyl ethyl ammonium ion, trimethyl ethyl ammonium ion, trimethyl propyl ammonium ion, trimethyl hexyl ammonium ion, and tetrapentyl ammonium ion, but is not limited to them alone.

The alkyl pyridium ion includes N-methyl pyridium ion, N-ethyl pyridinium ion, N-propyl pyridinium ion, N-butyl pyridinium ion, 1-ethyl-2methyl pyridinium ion, 1-butyl-4-methyl pyridinium ion, and 1-butyl-2,4 dimethyl pyridinium ion, but is not limited to them alone.

These room temperature molten salts having cation can be used either alone, or as mixture of two or more types.

The imidazolium cation having the skeleton shown in chemical formula (2) will be explained below. The dialkyl imidazolium ion includes 1,3-dimethyl imidazolium ion, 1-ethyl-3-methyl imidazolium ion, 1-mehyl-3-ethyl imidazolium ion, 1-methyl-3-butyl imidazolium ion, 1-butyl-3-methyl imidazolium ion. The trialkyl imidazolium ion includes 1,2,3-trimethyl imidazolium ion, 1,2-dimethyl-3-ethyl imidazolium ion, 1,2-dimethyl-3-propyl imidazolium ion, and 1-butyl-2,3-dimethyl imidazolium ion, but is not limited to them alone.

These room temperature molten salts having cation can be used either alone, or as mixture of two or more types.

5) Case

A case can be a metal case or a laminate film case.

The metal case can be a metal can made of aluminum, aluminum alloy, iron, stainless steel or the like, in square or cylindrical shape. The plate thickness of the case is preferred to be 0.5 mm or less, or more preferably 0.2 mm or less. The lower limit is preferred to be 0.05 mm.

A laminate film is, for example, a multilayer film including metal foil coated with a resin film. The resin includes polypropylene (PP), polyethylene (PE), nylon, polyethylene terephthalate (PET), and other polymer. A preferred thickness range of the laminate film is 0.2 mm or less. A preferred lower limit of the thickness is 0.05 mm.

The nonaqueous electrolyte battery according to the invention can be applied in nonaqueous electrolyte batteries of various shapes including the prismatic type, cylindrical type, flat type, sheet type, coin type, and the like. An example of a flat type nonaqueous electrolyte battery will be shown in FIGURE 1.

This nonaqueous electrolyte battery comprises a bag-shaped film case 6, an electrode group accommodated in the film case, and a nonaqueous electrolyte held by the electrode group. The electrode group comprises a positive electrode 3, a negative electrode 4 and a separator 5 provided between the positive electrode 3 and the negative electrode 4. The electrode group has a structure in which the positive electrode 3, the negative electrode 4 and the separator 5 are flatly wound. This electrode group is manufacture, for example, by flatly winding the positive electrode 3 and negative electrode 4 with the separator 5 interposed therebetween, and pressing and heating. In the electrode group, the positive electrode 3 and the negative electrode 4 can be adhere to the separator 5 by an adhesive polymer. The belt-like positive electrode terminal 2 is connected to the positive electrode 3 at one end, and is drawn outside of the case at the other end. One end of the belt-like negative electrode terminal 1 is connected to the negative electrode 4, and the other end is drawn outside of the case.

The nonaqueous electrolyte secondary battery according to the embodiment of the invention can be used as any charging and discharging system, for example, a power source of a control system for a driving motor of an electric car.

Examples of the invention are described below by referring to the above drawings, but it must be noted, however, that the invention is not limited to these embodiments alone as far as not departing from the scope of the invention.

EXAMPLE 1

A battery having the structure shown in FIGURE 1 was fabricated. Examples 2 to 4 and Comparative examples 1 to 4 are same in structure as shown in FIGURE 1.

<Preparation of Positive Electrode>

By blending 90 wt. % of lithium cobalt oxide (LiCoO2) as an active material, 3 wt. % of acetylene black, 3 wt. % of graphite, and 4 wt. % of polyvinylidene fluoride (PVdF) in n-methyl pyrrolidone (NMP), a slurry was prepared. The slurry was applied on both sides of a current collector made of an aluminum foil of 15 μm in thickness, and dried and pressed, and a positive electrode with electrode density of 3.0 g/cm3 was prepared.

<Preparation of Negative Electrode>

By blending Li4Ti5O12 as a negative electrode active material, coke with average particle size of 1.12 μm and specific surface area of 82 m2/g as an electronic conductor, and polyvinylidene fluoride (PVdF) by a ratio of 90:5:5 by weight, the mixture was dispersed in n-methyl pyrrolidone (NMP) solvent, and a slurry was prepared. The obtained slurry was applied on an aluminum foil of 15 μm in thickness, and dried and pressed, and a negative electrode was prepared. In the coke used herein, the spacing (d002) of (002) plane was 0.3504 nm, and the crystallite size (Lc) in the C-axis direction was 1.89 nm. The working potential of this electrode was nobler 1.55 V than the lithium electrode potential. That is, the working potential of this electrode was 1.55 V vs. Li/Li+.

<Preparation of Electrode Group>

The positive electrode, a separator of a porous film made of polyethylene of 25 μm in thickness, the negative electrode, and the separator were laminated in this sequence, and wound spirally. By heating and pressing at 90 C., a flat electrode group of 30 mm in width and 3.0 mm in thickness was prepared. The obtained electrode group was put in a pack made of a laminate film that has a thickness of 0.1 mm and comprises an aluminum foil of 40 μm in thickness and a polypropylene layer formed at both sides of the aluminum foil. The electrode group contained in the pack was dried in vacuum at 80 C. for 24 hours.

<Preparation of Liquid Nonaqueous Electrolyte>

Ethylene carbonate (EC) and γ-butyrolactone (BL) were mixed by a ratio by volume (EC: BL) of 25:75. In the obtained mixed solvent, 1.5 mol/L of lithium tetrafluoro borate (LiBF4) was dissolved as an electrolyte, and a liquid nonaqueous electrolyte was prepared.

After pouring the liquid nonaqueous electrolyte into the laminate film pack containing the electrode group, the pack was completely sealed by heat seal, and a nonaqueous electrolyte secondary battery having the structure as shown in FIGURE 1, width of 35 mm, thickness of 3.2 mm, and height of 65 mm was prepared.

Similar nonaqueous electrolyte secondary batteries were manufactured in the same manner as in Example 1 except that the spacing (d002) of (002) plane and the crystallite size (Lc) in the C-axis direction of coke were changed as shown in Table 1. The obtained secondary batteries were stored in 85 C. environment for 24 hours thickness in a fully charged state, and changes of the battery thickness before and after storage were measured. Results are shown in Table 1, together with the results of other than Example 1.

TABLE 1
d002 (nm)
Lc (nm) 0.340 0.344 0.350 0.352 0.36
80 C C C C C
20 C C C C C
10 C A A A C
8 C A A A C
2 C A A A C
0.5 C A A A C
0.1 C A A A C
0.01 C B B B C
0.001 C B B B C

In Table 1, rank A shows the battery thickness changes after cycles of 3 % or less, rank B shows changes of more than 3% and 5% or less, and rank C shows changes more than 5%. The secondary battery in Example 1 was 3% or less in the battery thickness change, that is, rank A.

As clear form Table 1, by selecting the spacing (d002) of (002) plane of 0.344 nm or more and 0.352 nm or less and the crystallite size (Lc) in the C-axis direction within 10 nm or less, preferably 0.1 nm or more and 10 nm or less, it is understood that the battery having high safety and being suppressed in changes of the battery thickness can be presented.

Battery swelling in high temperature storage varies significantly depending on the surface state of the carbonaceous material to be used as an electronic conductor. To suppress battery swelling due to gas generation, it important to use a carbonaceous material having a proper crystallinity as an electronic conductor. Among them, a carbonaceous material having a crystallinity of the spacing (d002) of (002) plane of 0.344 nm or more and 0.352 nm or less is preferred. Since acetylene black having low crystallinity has a great quantity and variety of functional groups on the surface, it is high in reactivity with electrolyte, and gas is generated extremely. In the case of graphite or the like high in crystallinity, on the other hand, the edge surface of graphite is also high in reactivity with the electrolyte, and gas generation is promoted. Owing to this reason, in the case of the battery comprising the carbonaceous material having the spacing (d002) of (002) plane of 0.344 nm or more and 0.352 nm or less and the crystallite size Lc of 10 nm or less, even if exposed to high temperature environment, the battery is not swollen, and a stable characteristic can be maintained.

EXAMPLE 2

A nonaqueous electrolyte secondary battery same as in Example 1 was manufactured except that the electronic conductor was replaced by coke of which average particle size is 3.37 μm, specific surface area is 25.7 m2/g, spacing (d002) of (002) plane is 0.3472 nm, and crystallite size (Lc) in the C-axis direction is 1.90 nm.

EXAMPLE 3

A nonaqueous electrolyte secondary battery same as in Example 1 was manufactured except that the electronic conductor was replaced by coke of which average particle size is 5.87 μm, specific surface area is 12.7 m2/g, spacing (d002) of (002) plane is 0.3443 nm, and crystallite size (Lc) in the C-axis direction is 1.90 nm.

EXAMPLE 4

A nonaqueous electrolyte secondary battery same as in Example 1 was manufactured except that the negative electrode active material was replaced by iron sulfide (FeS).

COMPARATIVE EXAMPLE 1

A nonaqueous electrolyte secondary battery same as in Example 1 was manufactured except that the electronic conductor was replaced by acetylene black of which average particle size is 0.022 μm, specific surface area is 127 m2/g, spacing (d002) of (002) plane is 0.3553 nm, and crystallite size (Lc) in the C-axis direction is 1.12 nm, and that the negative electrode active material and the electronic conductor were mixed with polyvinylidene fluoride (PVdF) at a ratio by weight of 90:5:5 to prepare a negative electrode slurry.

COMPARATIVE EXAMPLE 2

A nonaqueous electrolyte secondary battery same as in Example 1 was manufactured except that the electronic conductor was replaced by graphite of which average particle size is 15 μm, specific surface area is 4.25 m2/g, spacing (d002) of (002) plane is 0.3356 nm, and crystallite size (Lc) in the C-axis direction is 100 nm, and that the negative electrode active material and the electronic conductor were mixed with polyvinylidene fluoride (PVdF) at a ratio by weight of 90:5:5 to prepare a negative electrode slurry.

COMPARATIVE EXAMPLE 3

A nonaqueous electrolyte secondary battery same as in Comparative example 1 was manufactured except that the negative electrode active material was replaced by iron sulfide (FeS).

COMPARATIVE EXAMPLE 4

A nonaqueous electrolyte secondary battery same as in Comparative example 2 was manufactured except that the negative electrode active material was replaced by iron sulfide (FeS).

In the prepared secondary batteries of Examples 1 to 4 and Comparative examples 1 to 4, discharge capacity maintenance rate at 1 C/0.2 C was measured, and charge and discharge cycle test was conducted.

The charge and discharge cycle test was conducted in the environment of 45 C. Charge and discharge were repeated at current of 1 CmA and in a voltage range of 1 to 3 V. The number of cycles reaching 80% of capacity from the initial capacity is determined as the end of cycle life. Results of the charge and discharge cycle test are summed up in Table 2.

TABLE 2
Charge and Battery
1C/0.2C discharge thickness
capacity cycle life change after
ratio (times) cycles (%)
Example 1 98 400  +2%
Example 2 98 350  +5%
Example 3 98 400  +3%
Example 4 98 300  +2%
Comparative 98 100 +300%
example 1
Comparative 90 250  +5%
example 2
Comparative 98 80 +350%
example 3
Comparative 90 200  +10%
example 4

As a result, in the batteries using the electronic conductor having a proper crystallinity, gas generation was suppressed as compared with batteries using carbon black, and the charge and discharge cycle life was longer. As compared with the batteries using graphite as an electronic conductor, the high rate characteristic was known to be superior. This phenomenon may be explained as follows. In the case of the carbonaceous material of large spacing such as acetylene black, acetylene black has a high reactivity to the electrolyte. Therefore, the electrolyte is reduced and decomposed on the surface of acetylene black, a large amount of gas is generated, so that the cycle life is shortened. In the case of the carbonaceous material of small spacing and large crystallite size such as graphite, reducing decomposition on the graphite surface is suppressed, but the favorable conductive network cannot be built, so that a high rate characteristic declines. On the other hand, by using the electronic conductor in Examples 1 to 4, the two characteristics can be established at the same time.

EXAMPLE 5

<Preparation of Negative Electrode>

By blending Li4Ti5O12 powder of which average primary particle size is 0.8 μm as a negative electrode active material, coke 1 having a particle size distribution as shown in Table 3 as an electronic conductor, and polyvinylidene fluoride (PVdF) by a ratio of 90:5:5 by weight, the mixture was dispersed in n-methyl pyrrolidone (NMP) solvent, and a slurry was prepared. The obtained slurry was applied on an aluminum foil of 15 μm in thickness, and dried and pressed, and a negative electrode was prepared. In the coke used herein, the spacing (d002) of (002) plane was 0.350 nm, and the crystallite size (Lc) in the C-axis direction was 1.89 nm.

The working potential of this electrode was nobler 1.55 V than the lithium electrode potential. That is, the working potential of this electrode was 1.55 V vs. Li/Li+.

<Preparation of Electrode Group>

The positive electrode same as in Example 1, the separator same as in Example 1, the negative electrode, and the separator were laminated in this sequence, and wound spirally. By heating and pressing at 90 C., a flat electrode group of 30 mm in width and 3.0 mm in thickness was prepared. The obtained electrode group was put in a pack made of a laminate film of 0.1 mm in thickness, and dried in vacuum at 80 C. for 24 hours.

The same liquid nonaqueous electrolyte as in Example 1 was poured into the laminate film pack containing the electrode group, the pack was completely closed by heat seal, and a nonaqueous electrolyte secondary battery of the same structure as in FIGURE 1 with 35 mm in width, 3.2 mm in thickness, and 65 mm in height was fabricated.

EXAMPLES 6 TO 14

Nonaqueous electrolyte secondary batteries same as in Example 5 were manufactured except that cokes 2 to 10 of which particle size distribution is as shown in Table 3 were used.

In the obtained secondary batteries of Examples 5 to 14, a high rate characteristic was measured. The index of the high rate characteristic is the ratio of 5 C current discharge capacity to 0.2 C current discharge capacity.

TABLE 3
Type of
electronic D10 D50 D90
conductor (μm) (μm) (μm) 5 C/0.2 C (%)
Example 5 Coke 1 0.56 1.12 2.99 33
Example 6 Coke 2 0.54 1.15 3.42 45
Example 7 Coke 3 0.89 2.54 4.81 51
Example 8 Coke 4 2.55 5.37 11.7 82
Example 9 Coke 5 2.69 6.05 12.9 90
Example 10 Coke 6 4.68 12.8 22.2 91
Example 11 Coke 7 5.04 11.8 21.7 90
Example 12 Coke 8 9.03 15.7 28.0 75
Example 13 Coke 9 12.3 18.2 29.2 47
Example 14  Coke 10 13.3 22.1 35.6 23

As clear from Table 3, in the secondary batteries of Examples 8 to 12 having the electronic conductor with the particle distribution of D10 of 0.1 μm or more and 10 μm or less, D50 of 5 μm or more and 20 μm or less, and D90 of 10 μm or more and 30 μm or less, the ratio of 5 C current discharge capacity to 0.2 C current discharge capacity was higher than in the secondary batteries of Examples 5 to 7, 13, and 14.

The mean primary particle size of the negative electrode active material, the particle size distribution of the electronic conductor, the specific surface area, the spacing (d002), and the crystallite size (Lc) in the C-axis direction were measured in the following methods.

<Mean Primary Particle Size of Negative Electrode Active Material, Particle Size Distribution of Electronic Conductor>

To measure the particle size of active material and electronic conductor, a Laser Diffraction Particle Size Analyzer (model SALD-300 of Shimadzu Corporation) was used. About 0.1 g of sample was put in a beaker, a surfactant and 1 to 2 mL of distilled water were added, and stirred sufficiently, and the solution was poured into a stirring water bath. Light intensity distribution was measured 64 times at intervals of 2 seconds, the particle size distribution data was analyzed, and the 50% particle size (D50) of cumulative frequency distribution was determined as an average primary particle size for the active material. As for electronic conductor, from the particle size distribution data, 10% particle size (D10) of cumulative volume distribution, 50% particle size (D50) of cumulative volume distribution, and 90% particle size (D90) of cumulative volume distribution were determined.

<Specific Surface Area of Electronic Conductor by BET Method>

A measuring apparatus named Autosorb of Yuasa Ionics was used. The sample amount was about 0.5 g. The sample was pretreated by desertion at 120 C. for 15 minutes.

<Measurement of Spacing d002 of (002) plane of Electronic Conductor>

The spacing d002 of (002) plane was determined from the powder X-ray diffraction spectrum by a FWHM (full width at half-maximum) middle point method. At this time, Lorentz scattering or other scatter was not corrected.

<Measurement of Crystallite Size Lc of Electronic Conductor>

Crystallite size Lc was measured by an X-ray diffraction method. In measurement data by the X-ray diffraction method, CuKα was used as an X-ray source, and high purity silicon was used as a standard substance. The value of Lc was determined from the position and half-width of each diffraction peak. It was calculated by the FWHM middle point method.

As described herein, the invention provides a nonaqueous electrolyte battery excellent in charge and discharge characteristic in high temperature environment, and-high in safety and reliability.

Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US7261979Mar 9, 2005Aug 28, 2007A123 Systems, Inc.Providing a lithium secondary cell, charging the cell at a C-rate of at least 4C, wherein at least 95% state of charge is obtained in less than 15 minutes
US7348101Feb 7, 2005Mar 25, 2008A123 Systems, Inc.Lithium secondary cell with high charge and discharge rate capability
US7462425Sep 20, 2004Dec 9, 2008Kabushiki Kaisha ToshibaNonaqueous electrolyte secondary battery and battery module
US7482090Mar 24, 2005Jan 27, 2009Kabushiki Kaisha ToshibaNonaqueous electrolyte secondary battery
US7579114Sep 14, 2006Aug 25, 2009Panasonic CorporationMaking an anode for a nonaqueous electrolyte battery by coprecipitating oxides/hydroxides of lithium, nickel and manganese from an aqueous solution using a reductant or inert gas; drying, baking to obtain composite crystal oxide; high energy density; compact; stability; cost efficiency
US7582380Apr 8, 2004Sep 1, 2009Electrochemical Systems, Inc.Lithium-ion cell with a wide operating temperature range
US7582386Sep 21, 2005Sep 1, 2009Kabushiki Kaisha ToshibaNonaqueous electrolyte battery, battery pack and vehicle
US7595134Sep 19, 2005Sep 29, 2009Kabushiki Kaisha ToshibaNonaqueous electrolyte battery, lithium-titanium composite oxide, battery pack and vehicle
US7601463Jun 9, 2005Oct 13, 2009Kabushiki Kaisha Toshibanonaqueous electrolyte comprising a nonaqueous solvent of diethylene carbonate and at least one of ethylene carbonate or propylene carbonate; electrolyte including an imide lithium salt selected from Li(CF3SO2)2N, Li(CF3SO2)(C2F5SO2)N and Li(C2F5SO2)2N, excellent in high temperature cycle capability
US7629081Mar 24, 2005Dec 8, 2009Kabushiki Kaisha Toshibaexcellent in the high rate characteristics; rechargeable lithium batteries; dimethyl sulfite, diethyl sulfite, and methyl ethyl sulfite as electrolyte, and lithium titanium oxide and a carbonaceous material for negative electrode; use e.g. for camera or hybrid electric motor car
US7662515Oct 31, 2005Feb 16, 2010Kabushiki Kaisha Toshibacurrent collector supports negative electrode; lightweight
US7670723Sep 12, 2002Mar 2, 2010Panasonic CorporationComposite mixed oxide; concurrent precipitation
US7722989 *Nov 3, 2004May 25, 2010Panasonic CorporationNon-aqueous electrolyte secondary battery with a positive active material comprising primary particles and secondary particles made of the primary particles
US7745049Nov 18, 2008Jun 29, 2010Kabushiki Kaisha Toshibaanode current collector comprises aluminum (alloy) foil; anode active material particles include lithium titanium composite oxide particles; improved capacity and cycle performance in high temperature environment, rapid charging, and high rate discharging;
US7799461Aug 16, 2007Sep 21, 2010A123 Systems, Inc.Lithium secondary cell with high charge and discharge rate capability
US7803483Oct 28, 2005Sep 28, 2010Kabushiki Kaisha ToshibaHermetically sealed high capacity nonaqueous electrolyte battery and battery pack with the same
US7811703Mar 19, 2007Oct 12, 2010Kabushiki Kaisha Toshibabatteries comprising a negative electrode active material formed of lithium titanate having a spinel structure, and electrolytes containing solvents selected from the propylene carbonate, ethylene carbonate and gamma -butyrolactone; power sources for automobiles
US7820327 *Jan 17, 2008Oct 26, 2010Enerdel, Inc.Suitable for rechargeable power sources in gasoline electric motor hybrid vehicles; active material of Li4Ti5O12-x type having oxygen deficiency; performance
US7824800Jun 10, 2005Nov 2, 2010Electrochemical Systems, Inc.Contains electrolyte comprising a pyrazolium cation, an imidazolium cation, as well as lithium ion, and at least one non-Lewis acid derived counter-ion; ionic liquids; improved charge/discharge capacity and charging efficiency at low temperatures and high temperatures
US7829224Jan 21, 2010Nov 9, 2010Kabushiki Kaisha ToshibaNonaqueous electrolyte battery, battery pack and vehicle
US7833664Mar 19, 2007Nov 16, 2010Kabushiki KaishatoshibaBatteries comprising a negative electrode active material formed of lithium titanate having a spinel structure, and electrolytes containing solvents selected from the propylene carbonate, ethylene carbonate and gamma -butyrolactone; power sources for automobiles
US7858234Sep 12, 2006Dec 28, 2010Kabushiki Kaisha Toshibaincludes negative electrode containing a titanium oxide, a positive electrode, and a nonaqueous electrolyte; positive electrode includes a lithium-transition metal composite oxide and at least one kind of oxide selected from FePO4, Li3Fe2(PO4)3, LiFeP2O7, Fe4(P2O7) , Fe2(SO4)3, and v2o5; vehicles
US7883797Jul 13, 2005Feb 8, 2011Kabushiki Kaisha ToshibaNon-aqueous electrolyte battery
US7887955Jul 19, 2007Feb 15, 2011Kabushiki Kaisha Toshibabatteries comprising electrodes having a laminated structure in the anode and cathodes are alternately interposed between overlapped parts of a separator folded in a zigzag form
US7892674Sep 6, 2006Feb 22, 2011Kabushiki Kaisha ToshibaNonaqueous electrolyte secondary battery and battery module
US7892680May 13, 2010Feb 22, 2011Kabushiki Kaisha ToshibaNonaqueous electrolyte secondary battery and battery module
US7923152 *Mar 30, 2007Apr 12, 2011Kabushiki Kaisha ToshibaNonaqueous electrolyte battery, battery pack and vehicle
US7927740 *Oct 28, 2005Apr 19, 2011Kabushiki Kaisha ToshibaBattery pack and vehicle
US7960057 *May 16, 2005Jun 14, 2011Toyota Motor Engineering & Manufacturing North America, Inc.Battery with molten salt electrolyte and phosphorus-containing cathode
US7972730Oct 5, 2010Jul 5, 2011Kabushiki Kaisha ToshibaNonaqueous electrolyte battery, battery pack and vehicle
US8012627Jan 12, 2011Sep 6, 2011Kabushiki Kaisha ToshibaNonaqueous electrolyte secondary battery and battery module
US8039151Oct 25, 2005Oct 18, 2011Kabushiki Kaisha ToshibaNegative electrode active material, nonaqueous electrolyte battery, battery pack and vehicle
US8043739Dec 30, 2010Oct 25, 2011Kabushiki Kaisha ToshibaNonaqueous electrolyte secondary battery and battery module
US8088514Mar 25, 2005Jan 3, 2012Kabushiki Kaisha ToshibaNonaqueous electrolyte battery having a negative electrode active material with a lithium insertion potential of at least 0.2V (vs.Li/Li+) or formed of a lithium titanium oxide or a titanium-containing composite oxide
US8133619Jun 2, 2011Mar 13, 2012Kabushiki Kaisha ToshibaNonaqueous electrolyte battery, battery pack and vehicle
US8168330Sep 20, 2010May 1, 2012Enerdel, Inc.Lithium titanate cell with reduced gassing
US8313861Feb 8, 2012Nov 20, 2012Kabushiki Kaisha ToshiaNonaqueous electrolyte battery, battery pack and vehicle
US8313864May 8, 2009Nov 20, 2012Robert Bosch GmbhLi-ion battery with blended electrode
US8318351Jul 12, 2011Nov 27, 2012Kabushiki Kaisha ToshibaNonaqueous electrolyte battery containing a negative electrode of lithium-titanium composite oxide, battery pack and vehicle
US8349495Mar 24, 2006Jan 8, 2013Kabushiki Kaisha ToshibaNonaqueous battery with composite negative electrode
US8415053May 31, 2007Apr 9, 2013Kabushiki Kaisha ToshibaNonaqueous electrolyte battery, battery pack and rechargeable vacuum cleaner
US8426052May 8, 2009Apr 23, 2013Robert Bosch GmbhLi-ion battery with porous anode support
US8431271 *May 22, 2009Apr 30, 2013Gs Yuasa International Ltd.Positive active material for lithium secondary battery and lithium secondary battery
US8482262Apr 22, 2010Jul 9, 2013Kabushiki Kaisha ToshibaStorage battery system and automobile
US8541137Oct 24, 2012Sep 24, 2013Kabushiki Kaisha ToshibaNonaqueous electrolyte battery containing a negative electrode of lithium-titanium composite oxide, battery pack and vehicle
US8557443Oct 17, 2012Oct 15, 2013Kabushiki Kaisha ToshibaNonaqueous electrolyte battery, battery pack and vehicle
US8663850Nov 15, 2007Mar 4, 2014Kabushiki Kaisha ToshibaNonaqueous electrolyte battery, battery pack and vehicle
US20110068293 *May 22, 2009Mar 24, 2011Gs Yuasa International Ltd.Positive active material for lithium secondary battery and lithium secondary battery
US20110135982 *Jun 29, 2010Jun 9, 2011Yoshiyuki MuraokaNegative electrode for non-aqueous electrolyte secondary battery and fabrication method thereof, and non-aqueous electrolyte secondary battery
US20120121988 *May 14, 2010May 17, 2012Gs Caltex CorporationNegative active material for rechargeable lithium battery, method of manufacturing the same and rechargeable lithium battery having the same
US20120225346 *Sep 16, 2011Sep 6, 2012Keigo HoshinaNonaqueous electrolyte battery and battery pack
US20140072697 *Jul 1, 2013Mar 13, 2014Dainippon Screen Mfg. Co., Ltd.Method for manufacturing electrode for battery
EP2084765A2 *Nov 15, 2007Aug 5, 2009Valence Technology, INC.Secondary electrochemical cell with high rate capability
EP2115801A2 *Jan 17, 2008Nov 11, 2009EnerDel, Inc.Lithium titanate and lithium cells and batteries including the same
WO2005121413A2 *May 17, 2005Dec 22, 2005Michael ArmandBattery with molten salt electrolyte and phosphorus-containing cathode
WO2010129875A1 *May 7, 2010Nov 11, 2010Robert Bosch GmbhLi-ion battery with blended electrode
Classifications
U.S. Classification429/163, 429/221, 429/231.5, 429/231.8, 429/231.1, 429/231.95
International ClassificationH01M4/587, H01M4/131, H01M10/05, H01M4/36, H01M4/485, B82Y99/00, H01M2/00, H01M4/62, H01M2/26, H01M2/28, H01M2/02, H01M6/16
Cooperative ClassificationH01M4/625, H01M4/5815, H01M4/5825, H01M10/0587, H01M4/485, H01M6/16, H01M2/0287, H01M2300/0022, H01M4/581, H01M4/525, H01M4/364, H01M4/131, Y02E60/122, H01M4/136, H01M10/0525
European ClassificationH01M4/58B2, H01M4/36K1, H01M4/58D, H01M6/16, H01M4/485, H01M10/0525, H01M4/62C2
Legal Events
DateCodeEventDescription
Sep 20, 2004ASAssignment
Owner name: KABUSHIKI KAISHA TOSHIBA, JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:INAGAKI, HIROKI;TATEBAYASHI, YOSHINAO;TAKAMI, NORIO;REEL/FRAME:015811/0518
Effective date: 20040906